Light-sensitive emulsions containing non-migratory n-substituted 1-hydroxy-2-naphthamide color couplers



United States Patent 3,226,230 LIGHT-SENSITIVE EMULSIONS CONTAININGNON-MIGRATORY N-SUBSTITUTED l-HY- DROXY-Z-NAPHTHAMIDE COLOR COU- PLERSRaphael Karel Van Poucke, Mechlin, and Hector Alfons Van Den Eynde andArthur Henri De Cat, Mortsel- Antwerp, Belgium, assignors to GevaertPhoto-Producten N.V., Mortsel, Belgium, a Belgian company No Drawing.Filed Oct. 31, 1960, Ser. No. 65,883 Claims priority, applicationBelgium, Feb. 12, 1960, 39,565, Patent 587,525 2 Claims. (CI. 9655) Thisinvention relates to a process for the manufacture of photographic colorimages by color development in the presence of a color coupler, tophotographic material which contain such color couplers, and tophotographic images obtained according to the process referred to.

It is known to obtain a photographic color image by developing areducible silver salt image in the presence of a color coupler, i.e. acompound which during development couples with the oxidation product ofthe developing agent and forms a dyestufl on the area where the silversalt is reduced.

The modern methods of color photography are based upon the subtractivecolor principle according to which differently sensitized silver halideemulsion layers are superposed, each of them containing a color couplerwhich produces the subtractive yellow-, cyanand magenta-dyestufl imagesby development in a solution containing a primary aromatic amine.

Different demands are made upon the color couplers according to whetherthey are designed for negative or for positive material. Thus it isknown that l-hydroxy- 2-naphthamide color couplers, giving after thecolor development clear blue images, are preferably used for themanufacture of positive color materials. On the other hand it is desiredto use in the manufacture of negative materials al-hydroxy-Z-naphthamide color coupler which is developed to a cyanimage, the absorption spectrum of which is brought as much as possibleto the long wavelengths with side-absorptions as low as possible. Butthe disadvantage of the bathochromic shifting of the absorption centreis that this eflect is almost always accompanied by an increase ofunwanted side absorption viz. in the green and blue part of thespectrum.

To overcome this disadvantage there is a continuous research for cyancolor couplers with a bathochromically shifted absorption spectrumwhereby the side absorptions are kept as low as possible. In connectionherewith we refer to the color couplers which are manufactured accordingto the British patent specification 831,731.

It is an object of the present invention to provide a photographicmaterial containing a number of new color couplers.

It is another object of the present invention to provide a process toform a cyan dye color image in a lightsensitive silver halide emulsion.

Now it has been found that in the red light-sensitive silver halideemulsion of a photographic material, cyan color images are obtained withincreased transparency in the green by incorporating in said emulsion anaromatic N substituted 1-l1ydroxy-2-naphthoic acid amide color couplercorresponding to the following two formulae:

CONH

l X Y and wherein The new color couplers can be prepared by condensationof a l-hydroxy-Z-naphthoic acid or a derivative thereof with thearomatic amine desired. For the preparation of color couplers whichcontain in the naphthol or the anilide group a sulfonic acid group it isadvantageous to bring into the naphthol resp. anilide group before thecondensation a sulfofluoride group which after condensation issaponified to the corresponding sulfonic acid, e.g. by application ofthe method described in Belgian patent specifications 584,152 and590,934.

Hereinafter follows the preparation of some of these new color couplers.

1. Preparation of N-(o-cetylmercaptophenyl) lhydroxy-4-chloro-2-naphthoic acid amide:

15.42 g. of o-cetyl-mercaptoaniline-hydrochloride (prepared according toFarmaco (Pavia), Ed. pract., Ed. sci. 12, 206-17 (1957)), and 8.08 g. oftriethylamine are mixed with cm. of anhydrous benzene whereby agelatinous precipitate is formed. The reaction mixture is cooled off inice and 7 g. of o-phenylene chlorophosphite (prepared according toAnschiitz et al., Ber. 76, 1943/ 222) are dropwise added whereby theamount of precipitate increases. After stirring a certain time 8.9 g. of1-hydroxy-4-chloro'2-naphthoic acid are added and the new mixture isrefluxed for 20 min. This condensation is an application of the reactiontype described in J. Am. Chem. Soc. 74 (1952), 5304-9. The benzene isremoved by steam distillation. On cooling, the reaction mixture, a solidN-(o-cetylmercaptophenyl)-1-hydroxy-4- chloro-Z-naphthoic acid amide isformed in the aqueous layer of the mixture. This product is sucked offand washed with a sodium bicarbonate solution. To purify the product itis recrystallized from isopropanol. Melting point: 83-34 C.

II. Preparation of N(p-cetylmercaptophenyl)-1-hydroxy-4-chloro-2-naphthoic acid amide:

111 g. of p-mercapto-acetanilide (prepared according to J. Org. Chem. 15(1950) 405) and 203 g. of cetylbromide are dissolved in 825 cm. ofmethyl Cellosolve. This mixture is refluxed Whilst stirring whereafter40 g. of potassium hydroxide dissolved in cm. of methyl Cellosolve aredropwise added to the mixture. A potassium bromide precipitate is formedand after the addition of the potassium hydroxide the reaction mixtureis still refluxed whilst stirring for 30 min. whereafter 250 cm. ofwater are added thereto. The formed p-cetylmercaptoacetanilidecrystallizes and is recrystallized from a mixture of methanol and methylCellosolve. Melting point: 99-100 C.

29.3 g. of the synthetized (p-cetylmercapto-acetanilide) is refluxed for3 h. in 500 cm. of absolute ethanol with 5 equivalent of dried hydrogenchloride gas. On cooling the mixture, crystals ofp-cetylmercapto-anilinehydrochloride are formed. These crystals arerecrystal- 3 lized from a mixture of methanol and methyl Cellosolve.Melting point: 130-132 C.

14.75 g. of the hydrochloride and 7.75 g. of triethylamine are mixedwith 100 cm? of anhydrous benzene whereby a gelatinous precipitate oftreithylamine hydrochloride is formed. The reaction mixture is cooled bymeans of ice and 6.7 g. of o-phenylenechlorophosphite are dropwiseadded. The gelatinous precipitate of triethylamine hydrochlorideincreases and stirring is continued for a little while. Thereupon 8.5 g.of l-hydroxy- 4-chloro-2-naphthoic acid are added to the mixture, thenew mixture is refluxed for 20 min., the reaction mixture is poured intohot water, the benzene layer is washed with a saturated sodiumbicarbonate solution and hot water and the benzene is evaporated todryness under vacuum till a precipitate is formed which is composed of N(p-cetylmercaptophenyl)-1-hydroxy-4-chloro-2-naphthoic acid amide. Byadding n-hexane, the naphthoic acid amide is completely precipitated.The product is sucked ofi whereafter it is purified by recrystallizingfrom a mixture of methanol and methyl Cellosolve. Melting point: 110 C.

III. The preparation of N (2cetylmercapto-5-sulfophenyl)-1-hydroxy-4-chloro-2-naphthoic acid amidesodium salt is described in the Belgian patent specification 590,934(preparation 6).

IV. The preparation of N (2'cetylmercapto-5-sulfophenyl-1-hydroxy-4-bromo-2-naphthoic acid amidesodium salt is described in the Belgian patent specification 590,934(preparation 5).

V. The preparation of N-(3'-sulfo-4'cetylmercapto)phenyl-1-hydroxy-4-sulfo-2-naphthoic acid amide disodium salt isdescribed in the Belgian patent specification 590,934 (preparation 8).

To carry out the method according to the present invention, the colorcouplers must be incorporated into a photographic silver halide emulsionwhich in its turn is incorporated into a material having one or morelayers. The color couplers can be incorporated into said emulsions bymeans of the usual colloids such as gelatin, polyvinyl alcohol,collodium or other natural or synthetic colloids such as e.g. thoseprepared according to the Belgian patent specification 568,153. Thesilver halide emulsions can be applied to a support consisting of paper,glass, nitrocellulose, cellulose esters such as cellulose triacetate,polyester, polystyrene or an other natural or synthetic resin. Thismultilayer material is usually composed of the following layers: asupport, a red-sensitive emulsion layer having a color coupler for cyan,a green light-sensitive emulsion layer with color coupler for magentaand a blue-light sensitive emulsion layer having a color coupler foryellow. Between the blue-light sensitive and the green-light-sensitiveemulsion layer, there is a yellow filter layer which in most casesconsists of colloidal silver.

It is not only possible to incorporate the new color couplers into thelight-sensitive silver halide emulsion layer itself but they can also beincorporated into an adjacent non-light-sensitive colloid layer or intoa non-lightsensitive layer which is separated from the light-sensitiveemulsion layer by a water-permeable colloid layer.

The following aromatic amino-compounds can be used as developers forsuch material: mono-, diand triaminoaryl compounds, more especiallyN,N-dialkyl-p-phenylene diamine and its derivatives such asN,N-dialkyl-N'- sulphomethylor carboxymethyl p-phenylenediamine. Asuseful mono-amino-developer, aminophenols and aminocresols, or theirhalogen derivatives and also the aminonaphthols are considered.

The following examples illustrate the present invention withoutlimiting, however, the scope thereof. We draw the attention to the factthat all the amounts mentioned hereafter are parts of weight when noother indication is given.

Example 1 10 parts of N-[(2-cetylmercapto-5-sulfo)phenyl]-1-hydroXy-4-bromo-2-naphthoic acid amide sodium salt are wetted with 40parts of ethanol. The whole is dissolved by adding 20 parts of water andby heating at 40 C. This solution is diluted with Water up to 200 partstill obtaining a 5% solution. 200 parts of this color coupler solutionand 260 parts of Water are added to 500 parts of silver bromo-iodidegelatin emulsion (2% iodide). After adding the usual additives such ashardening agents and wetting agents the emulsion obtained is coated ontoa photographic support. After drying, the photographic material isexposed and treated with a developing solution of the followingcomposition:

G. N,N-diethyl-p-phenylenediamine hydrochloride 2.75 Sodium sulphite 2Potassium carbonate 75 Potassium bromide 0.5 Hydroxylamine hydrochloride1.2 Sodium hexametaphosphate 1.0

Water to 1000 cm.

This material is rinsed for 30 seconds and fixed in a fixing bath of thefollowing composition:

G. Sodium thiosulphate (dry) 200 Borax 8 Sodium sulphite 25 Potassiumalum 15 Boric acid 7.5

Water to 1000 cm.

Now the material is rinsed for 10 min. and bleached in a bath of thefollowing composition:

G. Potassium ferricyanide Potassium bromide 25 Borax 20 Boric acid 5Water to 1000 cm.

Finally the material is rinsed for 5 min. and fixed in a bath of thefollowing composition:

G. Sodium thiosulphate (dry) Sodium sulphite 10 Sodium carbonate 14Water to 1000 cm.

As a result of the foregoing treatments, an intense cyan image with lowside-absorptions in the green range is obtained.

Example 2 10 parts of N(2-cetylmercapto-5-sulfophenyl)-1-hydroxy-4-chloro-2-naphthoic acidamide sodium salt are wetted with 20 parts of ethanol dissolved into 180parts of water. Now the color coupler solution is incorporated into theemulsion according to Example 1. The material is exposed and treated inthe same way as described in Example 1. A cyan image is obtained whichshows loW side-absorptions.

Example 3 10 parts of N-(o-cetylmercaptophenyl)-1-hydroxy-4-chloro-2-naphthoic acid amide are wetted with 30 parts of ethanol anddissolved in 25 parts of 1 N sodium hydroxide and parts of water. Thecolor coupler solution is brought into the emulsion as described inExample 1. The emulsion is neutralized by 7.5 parts of acetic acid N/2per 100 parts of color coupler solution. After exposure, the material istreated according to Example 1 whereby in the color developing bath4-amino-N-ethyl- N (,8 methylsulfonamidoethyl)-rn-toluidinesesquisulphate monohydrate is substituted for N,N-diethyl-p-phen.-

ylenediamine hydrochloride. side-absorptions is obtained.

A cyan image with W Example 4 Example 5 200 cm. of a solution 5% ofN-(4-cetylmercapto-5- sulfophenyl) -1-hydroxy-4-sulfo-2-naphthoic aciddisodium salt (10 g. of color coupler dissolved in cm. of ethanol andcm. of sodium hydroxide N/ 2 diluted with water to 200 cm?) are added to500 cm. of a red-sensitized silver bromo-iodide emulsion (2% iodide).After acidification with acidic acid N/ 2 to a pH 6.5, the total volumeof the emulsion is brought to 1 1. This emulsion is coated onto asupport which alreay is coated with an anti'nalation layer. To thisemulsion layer is applied a gelatin intermediate layer on which iscoated a greenlight-sensitive emulsion layer with color coupler formagenta and covered with a yellow filter layer consisting of a thingelatin layer containing colloidal silver. On this filter layer is thencoated a blue-light-sensitive emulsion layer with a color coupler foryellow. This layer is coated with an antistress layer. The photographicmaterial obtained is dried, exposed and color developed according toExample 1. In this way an image with a subtractive color reproduction ofthe original is obtained which has an increased transparency in thegreen.

The term methyl Cellosolve is a registered trademark for (ethyleneglycol monomethyl ether) manufactured by Union Carbide and Carbon, NewYork, and is used in the foregoing specification.

We claim:

1. Process for obtaining a colored photographic image in a redlight-sensitive emulsion layer containing a reducible silver salt,comprising exposing said layer and developing same with a primaryaromatic amino developing agent in the presence of l-hydroxy-Z-naphthoicacid anilide color coupler for cyan selected from the group consistingof compounds having the formulae:

6 wherein X is selected from the group consisting of a bromine atom andchlorine atom,

Y represents a member selected from the group consisting of a hydrogenatom, a sulfonic acid group and a sulfonate group, and

R is a hydrocarbon radical having a chain length of about 5-20 carbonatoms and sufficient to render said color coupler resistant todifiusion.

2. Light-sensitive element comprising a red light-sensitive silverhalide emulsion layer and a l-hydroxy-Z-naththoic acid anilide colorcoupler for cyan for said layer, said color coupler being selected fromthe group consisting of compounds having the formulae:

X is selected from the group consisting of a bromine atom and a chlorineatom,

Y represents a member selected from the group consisting of a hydrogenatom, a sulfonic acid group and a sulfonate group, and

R is a hydrocarbon radical having a chain length of about 5-20 carbonatoms and sufiicient to render said color coupler resistant todiffusion.

References Cited by the Examiner UNITED STATES PATENTS 2,474,293 6/ 1949Weissberger et al 9655 2,979,405 4/1961 De Cat et a1 9655 2,993,7917/1961 Cole et al. 96--55 3,005,709 10/1961 Coles 9655 3,006,759 10/1961Loria et al. 96-55 3,013,879 12/1961 De Ramaix et al 9655 FOREIGNPATENTS 550,833 11/1956 Italy. 227,990 11/ 1943 Switzerland.

NORMAN G. TORCHIN, Primary Examiner.

PHILIP E. MANGAN, LOUISE P. QUAST, Examiners.

1. PROCESS FOR OBTAINING A COLORED PHOTOGRAPHIC IMAGE IN A REDLIGHT-SENSITIVE EMULSION LAYER CONTAINING A REDUCIBLE SILVER SALT,COMPRISING EXPOSING SAID LAYER AND DEVELOPING SAME WITH A PRIMARYAROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF 1-HYDROXY-2-NAPHTHOICACID ANILIDE COLOR COUPLER FOR CYAN SELECTED FROM THE GROUP CONSISTINGOF COMPOUNDS HAVING THE FORMULAE: